Flux for solder paste and solder paste

ABSTRACT

The flux for solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator, which prevents the skinning or changes by aging of viscosity. And at the actual use, the solder paste of the present invention can maintain good coating and printing ability for long time, further can endure the preheating under high temperature.

FIELD OF THE INVENTION

[0001] The present invention relates to a flux for solder paste and a solder paste characterizing that the changes in quality by aging are very small and can resist to preheating under high temperature.

DESCRIPTION OF THE PRIOR ART

[0002] The preparation method of a packaging substrate according to the following process is broadly practiced up to the present. That is, the solder paste is prepared by kneading a solder metal powder with a flux mainly composed of a rosin resin and derivatives thereof. Then said solder paste is coated and printed over the surface of a printed circuit and the necessary parts are installed, after that the soldering metal is fused by heating.

[0003] Recently, the parts to be installed to the packaging substrate which uses solder paste are becoming more compact and the packaging density of it is becoming higher, further the solder paste alloy itself is required to be lead free. Therefore, the requirement for the development of a solder paste which can maintain a good coating and printing adaptability for the long period and has good resistance to preheating under high temperature is becoming more serious. For the purpose to respond to the above-mentioned requirement, various discussions are continued and various proposals are provided. For instance, a creamy solder prepared by kneading a flux and a solder powder containing 0.01-6 wt. % of ring opened dicarboxylic acid or salt of it of carbon number 12 to 30 which is solid at normal temperature is disclosed in JP Patent Laid-open publication 6-63788. And in JP Patent Laid-open publication 2001-138089, zinc containing solder flux which contains fatty acid whose melting point is higher than 50° C. and organic halogenide whose melting point is higher than 100° C. and does not react substantially with zinc as an activator is disclosed. However, the products disclosed in these documents, are insufficient to satisfy the above mentioned current requirement.

[0004] The reason why the products disclosed in these documents are insufficient is because the mechanism of change in quality of the solder paste is greatly participated. That is, as the typical change in quality of the solder paste by aging, the “skinning” phenomenon can be mentioned. Said “skinning” phenomenon can be illustrated as follows, namely the viscosity of the solder paste is changed and hardened at the surface of solder paste and the surface becomes to look like to have a skin. Said change is caused by the reaction of the solder paste with oxygen or humid in atmosphere or by the reaction of an alloy contained in solder paste with an activator and an organic acid contained in flux. Said phenomenon can be avoided by reducing the changes in quality of the solder paste by aging, that is, by not using a halogenide activator or a conventional organic acid.

[0005] However, on the contrary, when these chemicals mentioned above are not used, it is difficult to maintain good soldering ability. Even if one of these abilities is satisfied, the total ability as a solder paste is not perfect. Therefore, the development of a solder paste which prevent the skinning phenomenon and the viscosity change by aging of solder paste, further can preserve good coating and printing ability for long term at the actual use and has a good resistance to preheating under high temperature has been expected.

THE OBJECT OF THE PRESENT INVENTION

[0006] The inventors of the present invention have carried out intensive study to develop the solder paste which prevents the skinning phenomenon and the viscosity change by aging of solder paste, further can preserve good coating and printing ability for long term at the actual use and has a good resistance to preheating under high temperature. And the inventors of the present invention have found out that the object can be solved by containing at least one of dicarboxylic acids of carbon number 3 to 5 and at least one of dicarboxylic acids of carbon number 15 to 20 as an activator in flux and accomplished the present invention. That is, the object of the present invention is to provide the solder paste which prevents the viscosity change by aging, can preserve good coating and printing ability for long term at the actual use and has a good resistance to the preheating under high temperature.

BRIEF SUMMARY OF THE INVENTION

[0007] The first important point of the present invention is a flux for solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator. The second important point of the present invention is a solder paste comprising a flux containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator and a solder alloy.

[0008] The action of the present invention is not yet made clear, however, the presumed action of the present invention can be illustrated as follows. Namely, a part of dicarboxylic acid of carbon number 3 to 5 contained in flux forms a salt with a metal which is a component of solder powder at the kneading process of the flux with the solder powder and coats the surface of solder powder and the changes in quality by aging such as viscosity change or the skinning phenomenon can be prevented by said coating action. In the meanwhile, since the reactivity of dicarboxylic acid of carbon number 15 to 20 is slow, it does not react scarcely with the solder powder at the kneading process of the flux and the solder powder, and does not have influence on the coating and printing process for long period or the preheating under high temperature, however, closely to the fusing temperature of the solder paste the function of it as an activator can be extracted sufficiently and displays good soldering ability. That is, by the synergistic effect of together use of these said dicarboxylic acids, the aimed object of the present invention can be accomplished.

DETAIED DESCRIPTION OF THE INVENTION

[0009] The present invention will be explained more in detail according to the following description.

[0010] As the concrete example of dicarboxylic acid of carbon number 3 to 5 used as an activator in the present invention, malonic acid, succinic acid, maleic acid, fumaric acid or glutaric acid can be mentioned. While, as the concrete example of dicarboxylic acid of carbon number 15 to 20, pentadecan di-acid (C₁₅H₂₈O₄), hexadecane di-acid (C₁₆H₃₀O₄), heptadecone di-acid (C₁₇H₃₂O₄), octadecane di-acid (C₁₈H₃₄O₄), nonadecane di-acid (C₁₉H₃₆O₄) or eicosanoic di-acid (C₂₀H₃₈O₄) can be mentioned. Particularly, the combination of succinic acid or malonic acid as the dicarboxylic acid of carbon number 3 to 5 and C₂₀H₃₈O₄ or C₁₆H₃₀O₄ as the dicarboxylic acid of carbon number 15 to 20 is desirable.

[0011] The amount of these dicarboxylic acids to be used are mentioned as follows. The amount of dicarboxylic acid of carbon number 3 to 5 is 0.05 to 5 wt. %. When the amount is smaller than 0.05 wt. %, the forming of coating film on the surface of solder powder is not perfect and the sufficient effect can not be expected, and when larger than 0.05 wt. % although the effect is good, the reliability of flux is deteriorated. Especially, when the amount of dicarboxylic acid of carbon number 3 to 5 is larger than 5 wt. %, it is difficult to maintain the good reliability. The desirable region of the amount of dicarboxylic acid of carbon number 3 to 5 is 0.1 to 3 wt. %.

[0012] The amount of dicarboxylic acid of carbon number 15 to 20 is 6 to 30 wt. %. When the amount is smaller than 6 wt. %, the amount of rosin becomes too small and causes the deterioration of tacking so that the sufficient printing ability can not be maintained. The desirable amount of dicarboxylic acid of carbon number 15 to 20 is 7-25 wt. %.

[0013] To the flux of the present invention, a thixotropic agent, a defoaming agent, an antioxidant, an anticorrosion agent, a surface active detergent or a thermosetting agent, which are used to the conventional flux, can be blended when the necessity is arisen. Namely, as a thixotropic agent to be added for the purpose to adjust the viscosity, hardened caster oil or fatty acid amide which are used to the ordinary flux can be used. The thixotropic agent can be blended in the limitation of smaller than 20 wt. % to the flux.

[0014] The solder powder alloy used in the solder paste of the present invention is the alloy containing metal such as Sn, Pb, Ag, Cu, In, Zn, Bi, Pd, Ni or Al. Concretely, a dualistic alloy represented by Sn—Pb, Sn—Ag, Sn—In or Sn—Zn or a triplicate alloy or more multiple alloy combined said dualistic alloy with one or more metals selected from the group consisting of Cu, Bi, In, Ni, Ge, Sb, Zn or Pb can be mentioned. Especially, in the case of Sn—Pb alloy, which is the Pb free alloy, the sufficient effect can be displayed.

EXAMPLES

[0015] The present invention will be illustrated more readily through the following Examples, however, not intended to limit the scope of the claims of the present invention to these Examples.

[0016] The changes by aging in qualities such as continuous printing ability, solder ball, wettability and viscosity of the solder paste are measured. The measuring methods are illustrated as follows.

[0017] {circle over (1)} Continuous printing ability: The printing is carried out continuously using a metal mask and block passing through ability and antiblotting ability are estimated. {circle over (2)} Solder ball: The solder paste is printed on a substrate, and after reflown the presence of solder ball is observed and inspected by a magnifying glass.

[0018] I . . . no solder ball

[0019] III . . . many solder balls are observed

[0020] {circle over (3)} Wettability: The solder paste is printed on a substrate and a part is mounted. After reflow, the wetting state of the part is observed by a magnifying glass.

[0021]502 . . . good

[0022] Δ . . . not wetted portion is observed

[0023] {circle over (4)} Viscosity: Measured according to JIS-Z-3284 standard using a Spiral viscosity meter PCU-205 (product of MARUCOM Co., Ltd.)

Example 1

[0024] weight part (%) Sn-3.0 Ag-0.5 Cu (25-45 μm) 90.0 Modified rosin 5.2 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Succinic acid (C₄H₆O₄) 0.2 Eicosanoic di-acid (C₂₀H₃₈O₄) 1.0 Ethylene glycol monobutylether 2.9

[0025] Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method.

[0026] Obtained results are shown in Table 1.

Example 2

[0027] weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 μm) 90.0 Modified rosin 5.5 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Malonic acid (C₃H₄O₄) 0.2 Hexadecane di-acid (C₁₆H₃₀O₄) 1.0 Ethylene glycol monobutylether 2.6

[0028] Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1. weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 μm) 90.0 Modified rosin 5.7 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Eicosanoic di-acid (C₂₀H₃₈O₄) 1.0 Ethylene glycol monobutylether 2.6

[0029] Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1. weight part (%) Sn-3.0 Ag-0.5 Cu(25-45 μm) 90.0 Modified rosin 6.0 Hardened caster oil 0.4 Cyclohexylamine hydrobrominate 0.3 Malonic acid (C₃H₄O₄) 0.2 Ethylene glycol monobutylether 3.1

[0030] Solder paste of above mentioned blending ratio is prepared and changes by aging in qualities of continuous printing ability, solder ball, wettability and viscosity are measured according to the above mentioned measuring method. Obtained results are shown in Table 1. TABLE 1 Initial date Viscosity continuous High temp. previous change (Pa · s) printing heating refrigerate ability solder ball wettability Initial 1 month 3 months Exmp.1 >16 hrs I ⊚ 200 210 197 Exmp.2 >16 hrs I ⊚ 185 192 192 Comp.  <8 hrs III Δ 194 245 370 Exmp.1 Comp. >16 hrs Insoluble insoluble 179 170 175 Exmp.2

EFFECT OF THE INVENTION

[0031] As mentioned above, the solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator is the solder paste which prevents the skinning or changes by aging of viscosity. And at the actual use, the solder paste of the present invention can maintain good coating and printing ability for long time, further can endure the preheating under high temperature. 

What is claim:
 1. A flux for solder paste containing dicarboxylic acid of carbon number 3 to 5 and dicarboxylic acid of carbon number 15 to 20 as an activator.
 2. The flux for solder paste of claim 1, wherein the content of dicarboxylic acid of carbon number 3 to 5.to the flux for solder paste is 0.05-5 weight %, and the content of dicarboxylic acid of carbon number 15 to 20 to the flux is 6-30 weight %.
 3. The flux for solder paste of claim 1 or 2, wherein dicarboxylic acid of carbon number 3 to 5 is succinic acid or malonic acid and dicarboxylic acid of carbon number 15 to 20 is eicosanoic di-acid (C₂₀H₃₈O₄) or hexadecane di-acid (C₁₆H₃₀O₄).
 4. A solder paste comprising the flux for solder paste according with anyone of claims 1 to 3 and a solder metal. 